Unsaturated polycarboxylic acidcellulose products and the process of making same



relented lion. as, i947 2 .11; STAT-E A PATENTQOQFFICE- 2,415,044 UNSATURATED roLYoAnBoxrLIo nom- CELLULOSE PlttUDUCTS AND THE PBOC- I ESS OF MAKING SAME John B. Rust, West Orange, N. 1., asslgn'or to Montclalr Research Corporation, a corporation .of New Jersey No Drawing. Application March 23, 1944,. l Serial No. 521,833

.. 11 Claims.

The present invention relates to cellulose derivatives andv to the process of making same. It is an object of this invention to provide clerivatives oi cellulose which are soluble in dilute alitalics. r I I lit is a further object of this invention to make availahlecellulose derivatives which are useful as textile sizing compositions.

It is an ohject of this invention to provide it is an object of this invention to provide paper sites and modifying agents.

Other objects and advantages will become anrare-ht iroru the more detailed description of the invention set forth hereinafter. Such detailed description should not be construed .as limiting, but only by way oi explanation and illustration, since numerous variations may be made by those skilledin the art without departing from the scope and spirit of the present invention.

The derivatives of the present invention may he formed by the reaction of an alkali cellulose derivative, as for instance soda cellulose, quaternary ammonium cellulose, potash cellulose, lithium cellulose, and the like, with alpha-beta unsaturated polycarboxylic acid compounds. The reaction may beeifected in the cold, in some instances, and in others by the application of heat.

Instances of alpha-beta unsaturated pclyoarlooxylic acid compounds which may be used in the process oi? the present invention are the ester, salt and ester-salt'derivatives oi maleic, lumaric, citraconic, ltaconic, glutaconic, methylene-melon ic, etc, acids such as diethyl maleate, monomethyl maleate, diethyl lumarate, dlallyl maleate, diailyl :lumarate, dlethyl ltaconate, dlallyl citraconate, diethyi rnethylene malonate, diethyl henzylidene malonate, and the like. I may first react cellulose with sodium hydroxide, for instance, to form soda cellulose. Alter aging the soda cellulosev to a satisfactory vlsoosltm'it is mixed, with cooling, with the ester of the alpha-beta unsaturated polybasic acid. l'teac tion is effected either in the cold, or the reaction mixture is allowed to Warm up "further heat ingapplied. I prefer to employ unsaturated nolyhasic acid esters which are alpha-beta unsaturated. I may also use substituted unsatu rated poly/basic acid esters. Thus, the alpha beta unsaturated acid esters or. salts of the (or. 106-197) z present invention may. be represented by the followlng' formulas; j

R coon" Renoir a o=o It two o 003'" and I R Bull C o o B" R coon" where R, R, R" and R"-may be allsyl, aryl,

allzarvl, oralkyl, oleflnyl, alkynyl, and the like or hydrogen, and R and R' may be hydrogen or an alkali metal. R"" is a divalent group. e. g.,

alkylene. Eitherthe-salts of the acids and of V the ester-acids or the free acid compounds can he used since the free (acid compounds form salts when added to the alkali cellulose. 4 Therefore, the unsaturated dibasic acid com pounds which are reacted with alkali cellulose include those compounds having the structural ro pi where any two'ot the lettered bonds are connected with a group which may be any monovalent organic radical or hydrogen. 0! the groups attached to the otherjtwo lettered bonds, both may be alkali carboxylates or monovalent organic radical carboxylates, or one may be-such a group and the other an alkali alkylenecarboxylate or monovalent organic radical alkylenecarboxylate.

In the reaction oi the present invention, it is suggested that reactions such as the following may occur. Representing. cellulose asCell-OH:

R- COOR' R- R" coon" Since rather strong alkaline conditions are employed, it is suggested thatsome saponiflcation of the esters may occur and the following be ob talned at least partially: v

' R R\ n coon cos-o-t-ouru and Ccll-0CG H000 00H 00011 The above is given by way of possible explana tion only and should not be construed as limiting since I do not wish to be limited by any theoretical explanation of the reaction of the present invention.

The cellulose derivatives are soluble in alkalies, with cooling, or not, according to the number and kind of substituted groups. Thus, I may make a derivative which is insoluble in alkali at ordinary temperatures but which is readily soluble by cooling the alkali suspension to about C. Such solutions are valuable as textile sizing agents. The solutions, usually of about 1% to strength, are applied to cotton, linen, or rayon goods on a padder, squeezed, dried and coagulated by using a solution of an acid, acid salt or a precipitating concentrated salt solution. The treated textile is washed thoroughly after coague lating and then dried. A firm hand is imparted to the fabric which is resistant to laundering and the ordinary cleansing agents. The finish may be applied at practically any convenient stage of processing such as before kier boiling, before dyeing and the like.

Since the derivatives of the present invention contain carboxyl groups they may be reacted with amines, etc., or dissolved in water in the form of their alkali metal salts. Furthermore, the materials may be precipitated in the form of the heavy metal salts such as the lead, zinc, aluminum, iron, etc., salt. The textiles sized with the derivatives of this invention may be dyed and the dyed textiles exhibit greater fastness to washing, laundering, and the like.

Cellulose in its various forms may be used in the present invention. However, after forming the alkali or quaternary ammonium cellulose, I prefer to age it to secure some controlled degradation until the desired viscosity is obtained. The viscosity may be varied both by using different forms and sources of cellulose, by introducing more or less reactant and by degrading the cellulose to a greater or lesser degree.

In the reaction of the present invention, use inert diluents, if desired, such as ethylene dichloride, carbon tetrachloride, benzene, ethyl ether, heptane, and the like. When making the alkali cellulose, concentrations of from to 50% of alkali may be used although greater or lesser concentrations can be employed. I usually prefer to employ concentrations of about 30% to 40%. This is also true of the quaternary ammonium hydroxides. When using these latter materials, solution of the cellulose sometimes occurs. In such, cases, the solutions may be diluted with alkali 'metal hydroxide solutions be- I may" fore reaction. Such quaternary ammonium hydroxides may be trimethyl benzyl ammonium hydroxide, tetraethyl ammonium hydroxide, diethyl dipropyl ammonium hydroxide, diethyl piperidinium hydroxide, methyl pyridinium hydroxide and the like.

The proportions of-reactants may be varied within very large limits of, for instance, from 5% to about 100% of the cellulose. For several reasons it may be desirable to use an excess of unsaturated polybasic acid. For instance, in some cases a more rapid reaction is desired and thus a greater proportion of the unsaturated acid should be used. The reaction may be terminated before completion, if desired.

As well as utilizing the unsaturated polybasic acid esters given above, I may also use alphabeta unsaturated acid esters or salts containing other negative substituents as, for instance, ethyl 0:0 R/ oooa' where R and R may be cyano, carboxy, carbalkoxy, aldehyde, acyl, and the like, as well as alkyl aryl, etc.

Therefore, the process of the present invention consists in allowing cellulose to react with an excess of a 15% to 50% (preferably about 30% to 40%) aqueous solution of an alkali such as sodium hydroxide to form alkali cellulose. The amount of alkali amounts to from 3 to about 8 moles per CeHmOs group of cellulose. To this mixture is then added from 5% to about (based on dry cellulose) of an alpha-beta unsaturated po lybasic acid ester or salt as above defined and reacted for a period from 1 to about 5 hours. The reaction temperature is between ice temperature and boiling, higher temperatures being employed when a degraded product (that is, one producing a lower viscosity) is desired, but in any case it is desirable to start the reaction at low temperatures. Afterwards the reaction mixture is acidified, whereby the product is coagulated and can be filtered, washed and dried. The dried product is capable of dissolving in dilute aqueous alkalies to form a homogeneous solution useful particularly as a wash-fast size for fabrics.

The following examples are given to illustrate the products and processes-of this invention. Parts are by weight.

Example 1.-66.5 parts of soda cellulose, containing 15 parts of cellulose and 51.5 parts of 33% sodium hydroxide solution, were mixed with 7.5 parts of diethyl maleate and 10 parts of water. The mixture was thoroughly homogenized and heated to 70C. for 2 hours. The product was acidified, washed with water, and dried. A white fibrous derivative which was soluble in dilute aqueous alkali on cooling, was obtained.

Example 2.68 parts of soda cellulose, containing 15 parts of cellulose and 53 parts of 33% sodium hydroxide solution, were mixed with 7.5 parts of diallyl fumarat'e and 30 parts of water. The mixture was homogenized and heated to 70 for 2 hours. The reaction product was acidified with acetic acid, washed, and dried. The product was a white fibrous mass soluble in dilute sodium hydroxide solutions on cooling.

Example 3.-68 parts of soda cellulose, containing 15 parts of cellulose and 53 parts of 33% sodium hydroxide solution, were mixed with 40 (I: I and RO O C 0 0 11 parts of a solution containing 8.1 parts of sodium maleate. The mixture was homogenized and heated at 6570 C. for 2 hours. The mixture was acidified with acetic acid, washed with water and acetone, and dried. A fibrous material was obtained which was soluble in sodium hydroxide solutions on cooling.

Example 4.-Monomethyl maleate was prepared by heating together 32 parts of absolute methanol with 98 parts of maleic anhydride to 60 C. for 1 hour then at 100 C. for 30 minutes. A solution of 40 parts of sodium hydroxide in 152 parts of water was poured into the monomethyl maleate to form the sodium methyl maleate. 24.6 parts of this solution containing an equivalent of 7.5 parts of maleicanhydride were mixed with 6'7 parts of soda cellulose, containing 15 parts of cel- 111105 and 52 parts of 33% sodium hydroxide dried.

5 i solution. The mixture was heated to 70 C. for 2 hours. A sample was removed (A); the mixture was heated for an additional hour and a sample removed (B); the mixture was heated for a further hour and a sample removed The last proportion was heated for an additional hour, making a total of hours. All samples were acidified, washed with water and acetone, and

ooocim \COOC2H5 and the mixture heated at 65 C. for 3 hours. The mixture was acidified, washed with water and acetone, and dried. A white fibrous material was obtained which dissolved in cold sodium -hydroxide solution, thereby yielding a thin solution.

Example 6.-67 parts of soda cellulose; containing 15 partsof cellulose and 52 parts of 33% sodium hydroxide solution, were mixed. with 75 parts of diethyl benzylidene malonate. The mixture was thoroughly homogenized and heated at 70 C. for 3 hours. acidified, washed with water and acetone, and A white fibrous product was obtained which dissolved in dilute sodium hydroxide solution on cooling.

Example 7.+-66. 5 parts of soda cellulose, containing 15 parts of cellulose and 51.5 parts of 33% sodium hydroxide, was mixed thoroughly with 7.5 parts of diallylitaconate. The mixture was then heated for 2 hours at 70 C. The reaction product was acidified, washed with water, and dried. A white fibrous derivative was obtained which was soluble in dilute aqueous alkali on cooling.

Example 8.-60 parts of soda cellulose, containing 15 parts of cellulose and 45 parts of 33% sodium hydroxide solution, were mixed with 7.5 parts of diallyl citraconate. The mixture was thoroughly homogenized and then subjected to a temperature of 65 C, for 3 hours. At the end oi this period the material was acidified, washed, and dried; A white fibrous product was thus obtained which proved to be soluble in dilute sodium hydroxid solution on cooling. A thin solution was obtained.

Example 9.-4 parts of the maleic-cellulose derivative of Example 1 were mixed with 30 parts of 33% sodium hydroxide solution, 70 parts of water, and 100 parts of crushed ice. A thin clear solution was obtained. A strip of cotton broadcloth was impregnated with the solution, squeezed and'dried. The broadcloth was treated in a 10% sulfuric acid solution to coagulate the cellulose derivative, then rinsed thoroughly in water, and dried. The fabric possessed a firm hand and the finish was not removed on repeated launderings;

I claim:

1. A cellulose derivative soluble in dilute aqueous alkali solutions comprising the reaction product of an alkali cellulose with a dicarboxylic The reaction product was acid compound containing the structural grouping where (1) any two of the lettered bonds are connected with groups selected from the class connected with groups selected from the the proportion of from 5% sisting of alkyl, aryl, alkaryl, aralkyl, olefinyl, alkynyl, cyano, carboxy, carbalkoxy, aldehydo and acyl radicals and hydrogen and (II) from 1 to 2 of the other two lettered bonds are con- 'class consisting of alkali carboxylates and alkyl carboxylates and, when one of said other lettered bonds is not connected with a group selected from said class, it is connected with a group selected from the class consisting of alkali alkylenecarboxylates and alkyl alkylenecarboiqrlates.

2. A cellulose derivative soluble in dilute aqueous alkali solutions comprising the coagulated, washed and driedreaction product of soda cellulose with a dicarboxylic acid compound containing the structural grouping and acyl radicals and hydrogen and (II) from 1 to 2 of the other two lettered bonds are connected with groups selected from the class consisting' of alkali carboxylates and alkyl carboxylates and, when one of-said other lettered bonds is not connected with a group selected from said class, it is connected with a group selected from the class consisting of alkali alkylenecarboxylates and alkyl alkylenecarboxylates; the dicarboxylic acid compound being reacted in to about 100% of the cellulose and the soda cellulose being pre pared from an aqueous sodium hydroxide solution of from 30% to 40% concentration with the amount of sodium hydroxide from 3 to about 8 moles NaOH per C6H10O5 group of cellulose.

3. A cellulose derivative soluble in dilute aqueous alkali solution comprising the reaction product of soda cellulose and diethyl maleate.

where (I) any two of the lettered bonds are connected with groups selected from the class consisting of alkyl, aryl, alkaryl, aralkyl, oleflnyl, alkynyl, cyano, carboxy, carbalkoxy, aldehydo and acyl radicals and hydrogen and (H) from 1 to 2 of the other two lettered bonds are connected where (I) any two of the lettered bonds are connected with groups selected from the class consisting of alkyl, aryl, alk'aryl, aralkyl, olefinyl, alkynyl, cyano, carboxy, and acyl radicals and hydrogen and (II) from 1 to 2 of the other two lettered bonds are connected with groups selected from the class consisting of alkali carboxylates and alkyl carboxylates and, 25

carbalkoxy, aldehydo a cellulose derivative when one of said other lettered bonds is not connected with a group selected from said class, it is connected with a group selected from the class' consisting of alkali alkylenecarboxylates and alkyl alkylenecarboxylates; the amount of dicarboxylic acid compound being from 5% to about 100% of the cellulose and the soda cellulos being formed from a sodium hydroxide solutionof from to concentration with the amount of sodium hydroxide from 3 to about 8 moles NaOH per C6H1005 group of cellulose.

'9. The process of making a cellulose derivative which is soluble in dilute aqueous alkali solutions which comprises reacting soda cellulose with diethyl maleate.

10'. The process of making a cellulose derivative which is: soluble in dilute aqueous alkali solutions which comprises reacting soda cellulose with diallyl maleate.

11. The process of making a; cellulose derivative which is soluble in dilute aqueous alkali solutions which comprises reacting soda cellulose with sodium monomethyl maleate.

- JOHN B. RUST. 

